DE102006049108A1 - Bioactive, ruthenium-containing coating and device - Google Patents

Abstract

The invention relates to the production and use of new bioactive devices and metallic coatings, for example for sterilization, disinfection and decontamination of water or aqueous solutions. In this case, the known oligodynamic effect of silver for germ reduction is improved and reinforced by the combination of silver with ruthenium and a vitamin or its derivative. The new properties of these bioactive metal surfaces result in faster and more efficient kill of microorganisms. At the same time, these new bioactive metal surfaces prevent colonization by microorganisms and the attachment or stable deposition of problematic biomolecules such as DNA, RNA or proteins. This results in a self-cleaning surface which, when in contact with water or aqueous solutions, very quickly and efficiently produces its sterility and maintains it over longer periods of time.

Description

The The present invention relates to a bioactive, ruthenium-containing Coating, especially for silver-containing surfaces, and a bioactive device having a silver and ruthenium containing surface as well the preparation and use of the bioactive coating and device.

By Ravelin and 1893 by Nägeli already described in 1869 the antibacterial effect of silver in very low dosages. The effectiveness of silver has not lost its relevance even today ( Landau, U. (2006): The germ-reducing effect of silver in hygiene, medicine and water treatment: the oligodynamics of silver; Isensee-Verlag, Oldenburg, 2006-10-03 ).

microbial Contaminations continue to cause major problems and commercial problems Losses in all areas related to water quality, aqueous solutions and hygiene stand. Such areas can be found, for example, in hospitals, hygiene institutes, in food technology, in production, in air conditioning technology and also in the household.

Nice longer There is therefore a wide variety of antimicrobial decontamination solutions aggressive chemicals against microorganisms, e.g. Formaldehyde, alcohols, phenols, sodium azide, sodium hypochlorite or strong oxidizing agents, e.g. Hypochlorite, bleach or mineral acid.

The Disadvantages of these solutions and methods are that for decontamination and disinfection used highly aggressive chemicals and oxidizing agents have a high corrosive and toxic potential. This will be treated water and watery Solutions for humans usually inedible and used devices or surfaces can corrosively damaged become.

Therefore Such aggressive chemical solutions are used for washing and rinsing Devices, Instruments and work surfaces usually in closed circuits used.

A gradual improvement of this problem brought the application of the Silver technology. The oligodynamic effect of silver allows the sterilization of water or aqueous solutions in a quality, the for is harmless to humans and protects materials and surfaces. The silver technology is therefore also used for drinking water in its production, Preparation and quality assurance used.

Therefore, work is constantly being done to improve the efficiency of silver technology. From the WO 2005/023206 A2 and the DE 100 54 248 A1 For example, more recent methods using nanoparticle properties to achieve accelerated release of silver ions over a very large surface are known.

The commercial interest in materials and methods of conservation the water quality or generally the quality aqueous solutions for the people about the Silver technology underlines the already broad commercial Sales of corresponding products among the most diverse Brand names.

The Disadvantages of the known methods for silver technology are a much delayed Use of the effect after contact of the silver with water and a only selective antibacterial effect. So it usually takes several Hours, often even much longer, until after contact of the silver with contaminated water, enough silver ions from the surface be released to a sufficient kill of the microorganisms and to achieve a sterilization of the water.

The Silver technology therefore has two problematic areas: 1. the time delayed Use of the germicidal Effect and 2. the limited spectrum of effects for efficient decontamination and disinfecting water or aqueous solutions for killing or Elimination of microorganisms and problematic biomolecules. Therefore, will constantly looking for improved methods and procedures to increase efficiency to increase the silver technology.

The new findings of modern molecular biology and genetic engineering also show that, in addition to microorganisms, hereditary information alone, individual genes or even parts thereof, as well as certain proteins are sufficient to cause diseases or to cause undesirable genetic changes ( Elhafi et al., 2004 ). Therefore, efficient decontamination of surfaces to kill or eliminate active biomolecules would be an additional safety benefit in all areas of water quality and hygiene.

Therefore In practice there is a need for improved materials, methods and methods for efficient and above all non-toxic and non-corrosive complete Decontamination and disinfection of water or aqueous solutions to kill or removal of microorganisms and active biomolecules, such as for example, DNA, RNA and proteins.

It is therefore an object of the present invention, the disadvantages of Prior art overcome and to develop new materials and processes that improved and achieve extended effect of silver technology.

These Task is inventively characterized solved, that the silver- and ruthenium-containing surface of the bioactive device additionally at least a vitamin or at least one derivative of a vitamin, at least a surfactant and / or at least one divalent or trivalent metal ion.

The Task is further according to the invention solved a bioactive coating, which at least ruthenium and in addition at least one vitamin or at least one derivative of a vitamin, at least one surface-active Substance and / or at least one divalent or trivalent metal ion includes. The coating according to the invention can advantageously either additional silver or, in place of ruthenium, silver-ruthenium-bimetallic particles or on a silver-containing surface of a device or another object.

The Rutheniummoleküle on the silver surface or in direct contact with silver molecules serve for faster Release of silver ions but at the same time as "anchor points" for the bond and complexing of vitamins or their derivatives, i. for example of ascorbic acid molecules or their derivatives.

The Task is about it by a method of making a bioactive device solved, namely by providing a device with a silver and ruthenium-containing surface, or applying a ruthenium coating on a silver surface the device, or applying a silver coating on the Device and subsequently Applying a ruthenium coating on the silver coating, or applying ruthenium-silver particles on the device; and applying at least one vitamin or at least one derivative of a vitamin, at least one surface-active Substance and / or at least one divalent or trivalent metal ion on the silver and ruthenium-containing surface of the device.

Further The object is achieved by a method for coating a device solved, namely by the application of a ruthenium coating on a silver-containing surface the device, or applying a silver coating on the device and subsequently Applying a ruthenium coating on the silver coating, or applying ruthenium-silver particles on the device; and applying at least one vitamin or at least one derivative of a vitamin, at least one surface-active Substance and / or at least one divalent or trivalent metal ion on the silver and ruthenium-containing surface of the device.

In The present invention is the known oligodynamic Effect of silver for germ reduction significantly improved and strengthened by the combination of silver with ruthenium and a vitamin, preferably ascorbic acid or their derivatives. These new bioactive metal surfaces lead to a faster and more efficient kill of microorganisms. simultaneously prevent these new metal surfaces colonization with microorganisms and the attachment or stable deposition of biomolecules, such as DNA, RNA or proteins. So get you have a self-cleaning surface when in contact with water or aqueous solutions very fast and efficient germ-free and generated over longer periods of time.

at the invention with too using silver-containing surface or silver surface can it is the surface a corresponding compact or solid material act. The device according to the invention However, in principle, any other material (such as e.g. Plastic, ceramics, glass, etc.) with an applied, thin, silver-containing Coating, which together with the applied outer ruthenium coating an effective ruthenium-silver sandwich system with a silver or silver alloy underlayer or backing and a moisture or wet-permeable ruthenium outer layer, -Oberschicht or -Deckschicht forms.

The coatings according to the invention or Coating systems, i. the ruthenium coating and an optionally required silver underlayer (i.d.R., having a thickness of 2-10 μm) are preferred applied galvanically or deposited. Other coating methods, such as PVD, CVD, sputter, sol, gel and reduction methods also for this suitable plating method.

The application of the ruthenium coatings is in this case controlled so that the silver-containing surface by continuous, preferably finely formed, free surfaces, openings, pores, cracks, gaps or the like in the ruthenium coating in moisture contact with the environment or in a moisture contact with the environment can be reached and thus a moisture contact between silver and the ruthenium is ensured. If the silver surface is occupied by ruthenium clusters, the oligo dynamic effect of silver can be enhanced in an advantageous manner. The preferably cluster-shaped, porous or microcracked, ruthenium layers in combination with silver allow a much more efficient release of silver ions into the environment. Preferably, ruthenium is applied to a thickness in the nanometer or micrometer range, with a thickness of at most about 2 .mu.m, in particular about 0.05 .mu.m and at least about 0.005-0.01 microns has proven particularly useful.

It can but also Ag-Ru particles are used in which silver and Ruthenium in electrically conductive contact and moisture or Water wet both metals. The silver-ruthenium bimetallic particles can in the micron or nanometer range, preferably in the nanometer range with a size of about <50 nm. Silver and ruthenium particles can also be effective as a single particle when a close metallic contact between both types of particles is given.

Nano- and micrometer-sized metal particles can be prepared, for example, by grinding, electrochemical, chemical reductive, capillary electrophoresis, hydrothermal synthesis, PVD, CVD or sol-gel methods. Ruthenium silver nanoparticles ( Wu et al., 1990 II ), Platinum ruthenium ( Schmidt et al., 1998 ), Ruthenium-copper ( Wu et al., 1990 I ) and ruthenium gold ( Wu et al., 1990 II ) are preferably prepared in the prior art for catalytic purposes.

The Electrodeposition, in particular the deposition of the inventive, preferably cluster-like, porous or microcracked, ruthenium layers, can by selection a suitable electrolyte, the metal content in the electrolyte, the electrolyte temperature, the pH of the electrolyte, the deposition time or treatment time and / or over the current density or amount of electricity can be specifically controlled. So are in particular also the structure and the dimensioning of the ruthenium clusters according to the invention, (Micro) pores and microcracks in the ruthenium layer through the selected determined by galvanic deposition conditions, so that the thickness and the structure of the ruthenium layer can be adjusted as needed or customizable and optimally adaptable to the respective application is. When galvanic deposition is not just a simple and known conventional Litigation usable, wherein the individual layers of a ruthenium-silver sandwich system according to the invention can be deposited one after another, but it is too commercially available, known and proven electrolyte systems can be used for this purpose.

Surfaces become before coating preferably first cleaned and a pickling and / or a rinse subjected. In the case of a non-electrically conductive device must be the surface the device before applying a silver and ruthenium coating pretreated according to the method known to a galvanic Be sure to apply a strong coating of silver and ruthenium to enable.

One first indication of the particular synergistic interaction between Ruthenium and ascorbic acid The finding indicates that ruthenium is very efficient in new decontamination solutions Vitamin derivatives, metal ions and detergents are used can.

It were new solutions and methods with divalent or trivalent metal ions, vitamin derivatives and detergents that have the disadvantages of the prior art for universal Overcome disinfection and decontamination solutions and not with aggressive, working with corrosive chemicals or strong oxidizing agents and also the treated substrates at room temperature or slightly elevated temperatures completely decontaminate.

It is known that in physiological amounts of micromolar concentrations, antioxidants in combination with divalent metal ions may occasionally lead to damage and partial strand breaks in nucleic acid molecules ( Padayatty et al., 2003 ; Blokhina et al., 2003 ; Veal et al., 1991 ). However, these are only isolated, isolated results that are only applicable to the individual case.

The systematic testing of new combinations of metal ions, vitamin derivatives and detergents has led to the development of highly efficient, universal, new decontamination and disinfection solutions. Further recent experiments prove that ruthenium also has a very efficient synergistic effect in this system (see 1 ).

Surprisingly, however, it was then additionally found that the incubation of newly developed silver and ruthenium-coated metal surfaces in ascorbic acid solutions leads to spontaneous binding and complexing of the ascorbic acid molecules to the ruthenium molecules. This forms a sustainable depot of ascorbic acid molecules on the metal surface. It is also possible a side by side silver and ruthenium coating, as long as a metallic contact is given. Also conceivable is a porous, microcracked silver layer over a porous ruthenium layer, provided that a contact between the two metals is given by an aqueous solution. These newly developed coating systems of silver, ruthenium and ascorbic acid and / or two and / or trivalent metal ions of the 4th period and / or transition groups I, II and VIII of the Periodic Table and / or inert surfactants have completely new surprising properties.

The new properties of these metal surfaces lead to a much faster and more efficient killing of microorganisms than the prior art with the previous ones Materials and methods possible is.

Of the Comparison of different silver samples with silver / ruthenium coatings after an ascorbic acid treatment in the Efficiency for the germ killing make this clear.

Round silver plates 1.3 cm in diameter were electroplated with appropriate microporous coatings and then incubated for 24 hours in 0.5 M aqueous ascorbic acid solution. After incubation, the plates were washed twice with sterile water. Ascorbic acid-treated silver / ruthenium sheet (Ag / Ru) shows much faster germination than the comparative samples. For example, bacteria in a test culture are drastically reduced in germ count after just 2 to 20 minutes, or are even completely killed (see 2A to 2D ). After treatment with ascorbic acid, the various comparative samples with pure silver plate (Ag), silver plate with gold coating (Ag / Au) or silver plate with palladium and nickel coating (Ag / Pd / Ni) only show contact and contact time after about 60 minutes the first significant decreases in bacterial count without achieving complete killing of all germs during this period.

Repeated washing of the ascorbic acid-treated silver-ruthenium surfaces with sterile water does not significantly reduce the increased antibacterial activity (see US Pat 3A to 3D ). This shows that the ascorbic acid molecules on the surface of silver and ruthenium have sustained binding and form a depot. Furthermore, there is a special synergistic interaction between all three components.

at The deposit of ascorbic acid may be needed simply by applying it or even just wiping with an aqueous ascorbic acid solution again filled become. Alternatively, the filling of the depot also by reincubation in an ascorbic acid solution.

The complement of the depot of ascorbic acid by applying a thin Layer of ascorbic acid, Metal ions and detergents give the extra special Effect that now also nucleic acid molecules on contact with this surface fast and completely be reduced. A decisive new point for the sustainable Depot formation are the inventively preferred, cluster-shaped, porous or microcracked, ruthenium-silver layers that are efficient Support custody.

A disadvantage of the prior art for the silver technology but also in general for most bioactive surfaces is a lack of degradation function for problematic biomolecules, such as DNA, RNA or proteins. Our own investigations show that various plastic or metal surfaces have no or only a very limited decomposing effect on DNA molecules (see 4 ).

The particular synergistic effect of the new Ag / Ru coatings in combination with ascorbic acid, metal ions and detergents can be seen in studies on the stability of DNA molecules on surfaces coated in this way. When defined DNA samples are applied to these surfaces as contamination, agarose gel and electrophoresis analysis shows rapid, complete degradation within 30 minutes to 24 hours. Further analyzes with the very sensitive PCR technology show that the applied DNA molecules are no longer detectable after 30 minutes. please refer 6 ). A comparative sample on a plastic surface shows no DNA degradation during this period. Thus, the new bioactive surfaces have the additional new feature of a self-cleaning surface for problematic biomolecules.

One Another object of the present invention is the use the bioactive invention Devices, coatings and metal surfaces for manufacture and preservation the sterility of water or aqueous solutions to ensure hygiene and water quality.

Further advantageous embodiments The present invention results from the objects of Dependent claims.

The efficient effect of the new metal surfaces is all the more surprising as proven the respective individual components no comparable efficient Show effects.

Only the loading of metal surfaces or coatings of silver and ruthenium with at least one vitamin or its derivatives, and preferably also with additional di- or trivalent metal ions and / or detergents leads to a synergistic effect and to an accelerated, more efficient degerming of aqueous Lö and degradation of problematic biomolecules on these metal surfaces or coatings.

The to produce according to the invention metal surfaces or coatings therefore contain silver, ruthenium and preferably Ascorbic acid or their derivatives.

The preferably to be used according to the invention Vitamin or its salts or acidic derivatives are one or more Compounds and / or salts thereof selected from the group of water-soluble Vitamins with the properties of antioxidants, as preferably Vitamin C, riboflavin and niacin. It is administered in amounts of about 1 mM used to 1000 mM based on the total solution, preferably in amounts of about 10 mM to 100 mM.

A additional Increasing the effect can be made by applying thin layers ascorbic acid or their derivatives and additional surfactants Substances are achieved. In the invention with too using surfactant Substances are anionic, nonionic, amphoteric or cationic inert surfactants or suitable mixtures with each other or with each other. In particular, alkyl ether sulfates, alkyl and / or arylsulfonates, alkyl sulfates, amphoteric surfactants, betaines, alkylamidoalkylamines, alkyl-substituted amino acids, alkyl-substituted imino acids, acylated amino acids and amphoteric surfactant combinations. Basically all inert surfactants suitable. Inert means they are neither the synergistic solution yet influence the test result. According to the invention, anionic are preferred and nonionic surfactants.

she are used in amounts of about 0.1 to 10 wt .-% based on the total solution, preferably in amounts of about 0.2 to 0.5 wt .-%.

On the bioactive invention surfaces can additionally also two and / or the trivalent metal ions applied become. These are ions of the metals of the 4th period and / or subgroups I, II and VIII of the periodic system of elements. you will be in the form of their salts with organic and / or inorganic acids or bases used. According to the invention preferred are one or more compounds selected from the subgroup VIII, in particular iron, cobalt, nickel, copper or zinc.

she are used in amounts of about 1 mM to 100 mM, based on the total solution, preferably in amounts of about 5 mM to 10 mM.

On the bioactive invention surfaces can additionally even more usual inert Auxiliaries and additives are applied, such as suitable Buffer substances for setting a defined pH, such as Tris (tris (hydroxymethyl) aminomethane), MES (2- (morpholino) ethanesulfonic acid), HEPES (2- [4- (2-hydroxyethyl) -1-piperazinyl] -ethanesulfonic acid, MOPS (3- (N-morpholino) propanesulfonic acid), carbonates and Derivatives of succinic acid. These buffer substances are used in amounts of about 1 mM to 500 mM based on the overall solution used.

When Contact and contact time between bioactive metal surfaces according to the invention and water or aqueous solutions are about 5 to 20 minutes at room temperature or slightly elevated temperature generally sufficient for complete decontamination and Disinfection. However, the methods used can be varied and can adapted to the respective requirements.

The The present invention allows the development of new bioactive surfaces for sanitary applications and for producing high water quality through coatings Silver, ruthenium and ascorbic acid or their derivatives. This is a new leap in quality in the decontamination and disinfection by the silver technology achieved as a result of this a faster antimicrobial effect in Combination with sustainable long-term protection is possible. At the same time it prevents active biomolecules, such as DNA, RNA or proteins, stably attach to the surface.

The The invention is illustrated by the following exemplary figures and exemplary embodiments:

It shows the 1 the special synergistic effect between ruthenium and ascorbic acid on the example of the degradation of DNA molecules.

The 2A -D show the increased antimicrobial activity of the coatings according to the invention of silver, ruthenium and ascorbic acid in comparison with other silver samples according to the prior art.

The 3A -D show the same test as in 2 after the identical metal sheets out 2 washed again with sterile water and dried.

4 shows an analysis of the stability of DNA molecules on different surfaces.

5 shows an analysis of the efficient DNA degradation on the new metal surfaces with a special coating.

6 shows a PCR analysis of DNA samples after different contact times with the inventively coated new metal surfaces.

1 shows the special synergistic effect between ruthenium and ascorbic acid on the example of the degradation of DNA molecules. Identical aliquots of DNA plasmids (YEp351) were treated for 2 minutes with the solutions below to sample 1-7. Subsequently, the DNA samples were denatured and the single-stranded DNA molecules were gel-electrophoretically separated on an agarose gel (1%). After staining with ethidium bromide gives the listed images. The control shows the intact plasmid DNA after treatment with sterile water. When strand breaks are introduced, the molecular weight of the affected DNA molecules decreases. This can be determined in the gel by comparison with the control and with the molecular weight marker. In each case, 5 μg of DNA in 5 μl of sterile Tris buffer (1 mM, pH 8.0) were treated with 5 μl of the solutions given below to sample 1-7 for 2 minutes at room temperature. Subsequently, the samples were mixed with 5 μl of 100 mM Tris (pH 12), provided with bromophenol blue marker and denatured for 5 minutes at 95 ° C. The denatured samples were immediately cooled to 4 ° C and each aliquot applied with 1 ug DNA per gel track. The DNA was stained after gel electrophoresis in 1% agarose gel with ethidium bromide and photographed.

Information about the samples:

• M: DNA marker 1 kb ladder; K: control: DNA + 5 μl sterile H ₂ O; 1: 100 mM ascorbic acid + 10 mM FeCl ₃ ; 2: 10 mM ascorbic acid + 1 mM FeCl ₃ ; 3: 100 mM ascorbic acid + 10 mM RuCl ₃ ; 4: 10 mM ascorbic acid + 1 mM RuCl ₃ ; 5: 100 mM ascorbic acid + 10 mM AgNO ₃ 6: 10 mM benzoic acid; 7: 100 mM ascorbic acid

• Proben: 0: nur steriles H₂O; 1: reines Silberblech (Ag); 2: Silberblech mit Ruthenium (Ag/Ru), 3: Silberblech mit Gold Ag/Au); 4: Silberblech mit Palladium und Nickel (Ag/Pd/Ni); 5: 100 mM Ascorbinsäure, 10 mM FeCl₃, 6: 100 mM Ascorbinsäure, 10 mM RuCl₃, (5 + 6 je mit 0,3% SDS und 0,2% Tween 20).

The 2A -D show the increased antimicrobial effect of the new coatings of silver, ruthenium and ascorbic acid in comparison with other silver samples. The metal sheets (1.3 cm diameter) were incubated in 0.5 M ascorbic acid solution, then washed with sterile water and dried. After drying, the samples were in 1 ml of sterile water containing 10 ⁵ bacteria of the standard strain Escherichia coli RRI give. The number of live bacteria was determined after incubation for 1, 5, 20 and 60 minutes and is given as 10 ⁵ to 10 ⁰ .

• Samples: 0: only sterile H ₂ O; 1: pure silver plate (Ag); 2: silver plate with ruthenium (Ag / Ru), 3: silver plate with gold Ag / Au); 4: silver plate with palladium and nickel (Ag / Pd / Ni); 5: 100 mM ascorbic acid, 10 mM FeCl ₃ , 6: 100 mM ascorbic acid, 10 mM RuCl ₃ , (5 + 6 each with 0.3% SDS and 0.2% Tween 20).

• Proben: 0: nur steriles H₂O; 1: reines Silberblech (Ag); 2: Silberblech mit Ruthenium (Ag/Ru), 3: Silberblech mit Gold (Ag/Au); 4: Silberblech mit Palladium und Nickel (Ag/Pd/Ni); 5: 100 mM Ascorbinsäure, 10 mM FeCl₃; 6: 100 mM Ascorbinsäure, 10 mM RuCl₃, (5 + 6 je mit 0,3% SDS und 0,2% Tween 20).

The 3A -D show the same test as in 2 after the identical metal sheets out 2 washed again with sterile water and dried. After drying, the samples were again in 1 ml of sterile water containing 10 ⁵ bacteria of the standard strain Escherichia coli RRI. The number of live bacteria was determined after incubation for 1, 5, 20 and 60 minutes and is given as 10 ⁵ to 10 ⁰ .

• Samples: 0: only sterile H ₂ O; 1: pure silver plate (Ag); 2: silver plate with ruthenium (Ag / Ru), 3: silver plate with gold (Ag / Au); 4: silver plate with palladium and nickel (Ag / Pd / Ni); 5: 100 mM ascorbic acid, 10 mM FeCl ₃ ; 6: 100 mM ascorbic acid, 10 mM RuCl _3, (5 + 6 each with 0.3% SDS and 0.2% Tween 20).

4 shows an analysis of the stability of DNA molecules on different surfaces. In each case 50 .mu.l of a DNA solution (25 ng / μl) were added dropwise to the surfaces. Aliquots of 2 μl each were removed after 24 hours and analyzed in the analytical agarose gel. The DNA was stained after gel electrophoresis in 1% agarose gel with ethidium bromide and photographed. The control surface used was sterile plastic.

gel application:

• K:

  Control sample of plastic surface

  M:

  Marker / 1 kb conductor

  1:

  DNA sample from Ag to ascorbic acid

  2:

  DNA sample from Ag / Au after ascorbic acid treatment

  3:

  DNA sample from Ag / Ru after ascorbic acid treatment

  4:

  DNA sample of Pd / Ni after ascorbic acid treatment

5 shows an analysis of the efficient DNA degradation on the new metal surfaces with special coating. The Ag / Ru coating was additionally provided with a thin layer of ascorbic acid, metal ions and detergents. For this purpose, a solution with 100 mM ascorbic acid, 10 mM FeCl ₃ , 0.3% SDS and 0.2% Tween 20 was brought to the surface by brief immersion, draining and drying. Subsequently, 50 μl of a DNA solution (25 ng / μl) were dropped onto the surfaces. Aliquots of 2 μl each were taken after the indicated times and the DNA was stained after gel electrophoresis in 1% agarose gel with ethidium bromide and photographed. The control surface was steri les plastic material used.

gel application:

• M:

  Marker / 1 kb conductor

  K1:

  Control sample of plastic surface after 30 minutes

  K2:

  Control sample of plastic surface after 1 hour

  K3:

  Control sample of plastic surface after 4 hours

  K4:

  Control sample of plastic surface after 24 hours

  Ab1:

  DNA sample of the coated Surface after 30 minutes

  Starting at 2:

  DNA sample of the coated Surface after 1 hour

  From 3:

  DNA sample of the coated Surface after 4 hours

  From 4:

  DNA sample of the coated Surface after 24 hours

6 shows a PCR analysis of DNA samples after different contact times with the coated new metal surfaces. The Ag / Ru coatings were additionally provided with a thin layer of ascorbic acid, metal ions and detergents. For this purpose, a solution with 100 mM ascorbic acid, 10 mM FeCl ₃ , 0.3% SDS and 0.2% Tween 20 was brought to the surface by brief immersion, draining and drying. Subsequently, 50 μl of a DNA solution (0.1 ng / μl) were dropped onto the surface. 2 μl aliquots were taken after the indicated times and each pipetted into a 50 μl PCR reaction mix. The PCR reaction mix contains primer pairs for the amplification of the test DNA (scPCP1 gene of the yeast). Controls (+/-) indicate if the PCR reaction has been successful. A 780 base pair (bp) band of test DNA indicates that intact DNA molecules are still present for this gene. Upon complete removal or destruction of the test DNA, no amplified DNA bands are detectable in the gel.

The DNA was after gel electrophoresis in 1% agarose gel with ethidium bromide stained and photographed. As a control surface Sterile plastic material was used.

gel application:

• +:

  positive control the PCR reaction with test DNA

  -:

  negative control the PCR reaction without DNA

  M:

  Marker / 1 kb conductor

  K1:

  Control sample of plastic surface after 30 minutes

  K2:

  Control sample of plastic surface after 1 hour

  K3:

  Control sample of plastic surface after 4 hours

  Ab1:

  DNA sample from coated Surface after 30 minutes

  Starting at 2:

  DNA sample from coated Surface after 1 hour

  From 3:

  DNA sample from coated Surface after 4 hours

Literature:

• Blokhina O., Virolainen E., Fagerstedt K.V. (2003): Antioxidants, Oxidative Damage and Oxygen Depriviation Stress: a Review. Annals Botany 91: 179-194
• Elhafi, G., Naylor, C.J., Savage, C.E. and Jones, R.C. (2004): Microwave or autoclave treatments destroy the infectivity of infectious bronchitis virus and avian pneumovirus but allow detection by reverse transcriptase polymerase chain reaction. Avian Pathology 33, 3003-306
• Padayatty S.J., Katz A., Wang Y., Eck P., Kwon O., Lee J.H., Chief S., Corpe C., Dutta A., Dutta S.K., and Levine M. (2003): Vitamin C as an antioxidant: evaluation of its role in disease prevention. J. Am. Coll. Nutr. 1, 18-35
• Schmidt, T.J., Noeske, M., Gasteiger, H.A., Behm, R. J., Britz, P., Bönnemann, H. (1998): PtRu Alloy Colloids as Precursors for Fuel Cell catalysts. J. Electrochem. Soc. 145, 925
• Veal J.M., Merchant K. & Rill R.L. (1991): The influence of reducing agent and 1,10-phenanthroline concentration on DNA cleavage by phenanthroline + copper. Nucl Acids Res Vol. 19, no. 12, 3383-3388
• Wu, X., Gerstein, B.C., King, T.S. (1990) I: Characterization of Silica-Supported Cu Monometallic and Ru-Cu Bimetallic Catalysts by Hydrogen Chemisorption and NMR of Adsorbed Hydrogen. J. Catal. 121, 271-293
• Wu, X., Gerstein, B.C., King, T.S. (1990) II: Characterization of Silica-Supported Ru-Ag and Ru-Au Bimetallic Catalysts by Hydrogen Chemisorption and NMR of Adsorbed Hydrogen. J. of Catalysis 123, 43-49

List with explanation of the abbreviations in the figures:

• Ag:

  Argentum / Silver

  (Ag):

  pure silver sheet

  (Ag / Ru):

  Silver sheet with ruthenium coating

  (Ag / Au):

  Silver sheet with gold coating

  (Ag / Pd / Ni):

  Silver sheet with palladium and nickel coating

  EtBr:

  ethidium bromide

  K:

  control

  M:

  Molecular weight marker

  PCR:

  Polymerase Chain Reaction / Polymerase Chain Reaction

  RT:

  room temperature

  ru:

  ruthenium

  sC:

  Saccharomyces cerevisiae

  scPCP1:

  Saccharomyces cerevisiae Gene for processing of cytochrome c peroxidase

  SDS:

  Sodiumdodecylsulfate

  YEp351:

  Yeast Episomal plasmid

Claims (24)

Bioactive device having a silver- and ruthenium-containing surface, characterized in that the surface additionally comprises at least one vitamin or at least one derivative of a vitamin, at least one surface-active substance and / or at least one divalent or trivalent metal ion. Bioactive device according to claim 1, characterized that the silver- and ruthenium-containing surface is formed in such a way that silver ruthenium contacts in contact with moisture the environment. Bioactive device according to claim 1 or 2, characterized characterized in that the vitamin comprises at least one compound the group of water-soluble Vitamins with antioxidant properties or a salt or acid Derivative of this compound. A bioactive device according to claim 1, 2 or 3, characterized in that the vitamin is ascorbic acid or a derivative of ascorbic acid is. Bioactive device according to one of claims 1 to 4, characterized in that the metal ion is an ion of one of Metals of the 4th period and / or the subgroups I, II, or VIII the periodic system of the elements. Bioactive device according to claim 5, characterized in that that the metal in the form of its salt with an acid or Base is present. Bioactive device according to one of claims 1 to 6, characterized in that the surface-active substance at least a compound from the group of anionic, nonionic, amphoteric or cationic surfactants or a suitable mixture of these compounds is. Bioactive coating, especially for a silver-containing Surface, which at least ruthenium and in addition at least one vitamin or at least one derivative of a vitamin, at least one surface-active Substance and / or at least one divalent or trivalent metal ion includes. Bioactive coating according to claim 8, characterized in that that in addition Silver or, instead of ruthenium, silver-ruthenium-bimetallic particles includes. Bioactive coating according to claim 8 or 9, characterized characterized in that the vitamin is ascorbic acid or a derivative of ascorbic acid. Bioactive coating according to claim 8, 9 or 10, characterized in that the ruthenium-containing coating a Thickness of at least 5-10 nm and a maximum of 2 μm having. Bioactive coating according to one of claims 8 to 11, characterized in that the ruthenium-containing coating cluster-shaped, microporous and / or micro-cracked is formed. Method for producing a bioactive device by: Providing a device with a silver- and ruthenium-containing Surface, or applying a ruthenium coating on a silver-containing surface the device, or applying a silver coating on the Device and subsequently Applying a ruthenium coating on the silver coating, or applying ruthenium-silver particles on the device; and Applying at least one vitamin or at least one derivative of a vitamin, at least one surface-active Substance and / or at least one divalent or trivalent metal ion on the silver and ruthenium-containing surface of the device. A method of coating a device by: applying a ruthenium coating to a silver-containing surface of the device, or applying a silver coating to the device, and then applying a ruthenium coating to the silver coating, or applying ruthenium-silver particles the device; and Applying at least one vitamin or at least one derivative of a vitamin, at least one surfactant, and / or at least one divalent or trivalent metal ion to the surface of the device comprising silver and ruthenium. The method of claim 13 or 14, wherein the silver coating and / or the ruthenium coating is / are designed such that these in a moisture contact with the environment is / stand. A method according to claim 13, 14 or 15, characterized characterized in that the ruthenium coating in a thickness of at least 5-10 nm and a maximum of 2 μm is applied. Method according to one of claims 13 to 16, characterized that a cluster-shaped, microporous and / or microcracked ruthenium coating is applied. Method according to one of claims 13 to 17, characterized that the silver coating is applied in a thickness of 2-10 microns. Method according to one of claims 13 to 18, characterized that the ruthenium and / or the silver coating by electrochemical, chemical-reductive, PVD, CVD, sputtering, reduction and sol-gel processes is / are made. Method according to one of claims 13 to 19, characterized that the silver-ruthenium particles as metal-bound bimetallic particles getting produced. Method according to claim 20, characterized in that that the bimetal particles are produced on the micrometer scale or nanometer scale, preferably <50 nm. Method according to one of claims 13 to 19, characterized that ruthenium and silver particles are produced as pure metal particles and for the preparation of silver ruthenium particles be brought into a close metallic contact. Method according to claim 22, characterized in that that the single metal particles of silver and / or ruthenium be prepared on a micrometer or nanometer scale, preferably <50 nm. Use of the bioactive device according to one the claims 1 to 7 and / or the bioactive coating according to one of claims 8 to 12 for the decontamination or disinfection of water or aqueous Solutions.